JPS63150270A - Diglycidyl ether of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane and production thereof - Google Patents

Abstract

NEW MATERIAL:Diglycidyl ether of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'- spirobiindane shown by formula I. USE:Useful as a curable composition component showing excellent characteristics such as chemical resistance, heat resistance and dimensional stability of cast material and applicable to epoxy resin fields. Readily curable with a generally known curing agent. PREPARATION:6,6'-Dihydroxy-3,3,3',3'-tetramethyl 1,1'-spirobiindane shown by formula II is reacted with an epihalohydrin in the presence of a dehydrohalogenating agent to give a compound shown by formula I. An alkali metallic hydroxide is used as the dehydrohalogenating agent and is preferably added in such a way that the reaction mixture maintains pH6.5-8.5. The ratio of the epihalohydrin used is 2-30 equivalents, preferably <=10 equivalents based on the compound shown by the formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides 6,6'-dihydroxy-3,3,3' i
Diglycidyl ether of 3'-tetramethyl-1,1''-spirobiindane and 6,6'-dihydroxy-
The present invention relates to a method for producing a novel diglycidyl ether having a basic structure of 3,33+,3+-tetramethyl-1,1°-spirobiindane (hereinafter abbreviated as SPI).

This glycidyl compound is expected to be applied in many fields such as casting and laminating paints because of its properties of providing a molding material by curing, crosslinking, and shaping.

(Prior art) Conventionally, the structures between epoxy groups are diverse, such as aromatic, alicyclic, and heterocyclic, but most of them are epoxy resins obtained by condensation of polyhydric alcohols such as bisphenol A and epichlorohydrin. A method is known in which a resinous product is obtained by mixing with a suitable curing agent and reacting the epoxy groups with these functional groups.

(Means for solving the problem) The product obtained by this method has excellent performance in terms of electrical properties, dimensional stability, and chemical resistance, but is still insufficient in terms of heat resistance. It is. Furthermore, these epoxy resins are required to have even higher performance.

The present inventors have conducted intensive studies to achieve the above objects and have completed the present invention.

That is, the present invention relates to 6,6'-dihydroxy-3,3,3'' represented by formula (I).
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Diglycidyl ether of 3'-tetramethyl-1,1'-spirobiindane and its decomposition with 6,6'-dihydroxy-3,3,3' and 3'-tetramethyl-1,1'-spirobiindane with epihalohydrin. This is a method for producing by reacting in the presence of a hydrogen halide agent.

The novel SPI diglycidyl ether of the present invention has a spiro ring in the structure between the epoxy groups, and has excellent chemical resistance, heat resistance, and dimensional stability of cast products.
It is characterized in that it is well compatible with commonly known curing agents and that curable compositions can be easily obtained.

The method for producing diglycidyl ether of SP1 of the present invention will be specifically explained.

That is, the compound of the present invention has S represented by the following formula (n)
It can be produced by reacting PI with epihalohydrin in the presence of a dehydrohalogenating agent.

This SPI can be easily produced by heat-treating 2,2-bis(4-hydroxyphenyl)propane in the presence of perfluoroalkanesulfonic acid, aliphatic sulfonic acid, or a strongly acidic resin (Japanese Patent Application No. 140-406-1982).
．． 60-149166.60-180500).

Glycidylation of organic compounds containing dihydroxy groups is a known transformation technique. That is, this reaction is expressed by formula (II)
The reaction is carried out by heating with SPI represented by the following formula and an epihalohydrin, preferably epichlorohydrin, to a temperature usually in the range of 40 to 120 DEG C., and further in the presence of a dehydrohalogenating agent.

The dehydrohalogenating agent of the present invention is particularly preferably an alkali metal hydroxide, such as sodium hydroxide. A dehydrohalogenating agent is added to the heated mixture of SPI and epihalohydrin to adjust the pH of the reaction mixture to about 6.5.
It is preferable to add gradually so as to maintain the temperature at 8.5.

The presence of additional solvent is usually not necessary as the epihalohydrin itself acts as a solvent. The proportion of epihalohydrin used in the reaction varies widely based on the hydroxyl content of the SPI and the degree of reaction desired. Usually 2
Epihalohydrin is used in an amount of up to 30 equivalents, preferably 10 equivalents or less considering economic efficiency.

Furthermore, if it is desired to remove excess dehydrohalogenating agent and by-product salts from the reaction product, washing is performed with water or other suitable solvent.

The reaction products produced by this method can also be cured with conventional curing agents.

Typical examples of hardeners are conventional hardeners for epoxy resins such as bis(4-aminophenyl)methane, aniline/formaldehyde resins, his(4-aminophenyl)sulfone, propane-1,3-diamine, hexa Methylenediamine, diethylenetriamine, triethylenetetramine, 2.2.4-trimethylhexamiso-1,6-diamine, m-xylylenediamine, bis(4-aminocyclohexyl), methane, 2.2-bis(4-amino cyclohexyl)propane and 3-aminomethyl-3,5,
Aliphatic, cycloaliphatic, aromatic and heterocyclic amines such as 5-trimethylcyclohexylamine (isophorone diamine); polyaminoamides such as those obtained from aliphatic polyamines and trimerization or trimerized fatty acids; resorcinol, hydroquinone, 2 .2-bis(4-hydroxyphenyl)
Polyphenols such as propane and phenol/aldehyde resins; polythiols such as those sold as "Thiocols"; e.g. phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, pyro These include mellitic anhydride, 3.3', 4.4''-benzophenonetetracarboxylic dianhydride, the acids of said anhydrides, and polycarboxylic acids and their anhydrides, such as isophthalic acid and terephthalic acid.

If the curing agent is a carboxylic acid or anhydride thereof, usually 0.4 to 1.1 equivalents of carboxyl group or anhydride group are used per equivalent of epoxy group. If the curing agent is a polyphenol, it is preferred to use 0.75 to 1.25 phenolic hydroxyl groups per equivalent of epoxy group.

Catalytic curing agent ranges from 1 to 40 parts by weight per 100 parts of epoxy.
section is commonly used.

(Functions and Effects) The novel SPT diglycidyl ether produced by the present invention is easily cured with a commonly known curing agent, and the cured resin has excellent properties in terms of heat resistance, chemical resistance, and dimensional stability. It can be expected to be applied to new epoxy resin fields.

In addition, the method of the present invention creates a new SP that has not been previously known.
The diglycidyl ether of I can be easily produced.

(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

Example 1 6゜6''-dihydroxy-3,3,3',3'-tetramethyl-1,1' was placed in a reaction vessel equipped with a stirrer, a thermometer, a Deannotak azeotropic distillation trap, and a dropping funnel.
- 15.4 g (0.5 mo+) of spirobiindane and 462.5 g (5.0 mol) of epichlorohydrin are charged and the slurry is heated to 95 DEG C. with stirring. A clear solution is obtained. Then, at this temperature, 110 g of 40% sodium hydroxide was added dropwise over 3 hours, followed by further stirring for 2 hours at 90-100"C. The product was then cooled, and 200 mt of methyl ethyl ketone was charged to the product, and chloride and After repeated washing with water until it does not contain a slight excess of sodium hydroxide, the solvent and epichlorohydrin are distilled from the organic layer by vacuum distillation, and then 189
g of brown resin is obtained. Epoxy content - 220 equivalents/K
g Softening point: 50°C Proton NMR solvent: Acetone-06 λ value: 1.36 (s), 1.44 (S) (CH3 group) 2.1,2 (CI2 group of C-1) 2.34 ( d) (CH2 at C-5) 2.6-2.84 (m) (CH group at C-6) 3.6
4-3.82 (m) (CHt group at C-7) 6.34
(d) (CH group at C-2) 6.82(q) (CH group at C-3) 7.18(d) (CI group at C-4) Elemental analysis value (χ) I Calculated value” 77 .14 7.62 Analysis value 7
5.94 7.56 ``SPI diglycidyl ether (A) produced in Example 1 as C2JzzOa, and liquefied MD^ (Epicure Z) as a curing agent.
) (B), acid anhydride type (Epicure YH-306)
(C) The curable mixtures listed in the table obtained from 2□4.6-tris(dimethylaminomethyl)phenol (T, 8, P) as accelerator are cast. The mechanical properties of the obtained cured product were tested. The test results are shown in the table.

Claims (2)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) 6,6'-dihydroxy-3,3,3'
, 3'-tetramethyl-1,1'-spirobiindane diglycidyl ether. (2) 6,6'-dihydroxy-3,3,3',3'-
6,6'-dihydroxy-3,3,3' characterized by reacting tetramethyl-1,1'-spirobiindane with epihalohydrin in the presence of a dehydrohalogenating agent.
, 3'-tetramethyl-1,1'-spirobiindane diglycidyl ether production method.